US4804719A - Water-dissipatable polyester and polyester-amides containing copolymerized colorants - Google Patents
Water-dissipatable polyester and polyester-amides containing copolymerized colorants Download PDFInfo
- Publication number
- US4804719A US4804719A US07/153,299 US15329988A US4804719A US 4804719 A US4804719 A US 4804719A US 15329988 A US15329988 A US 15329988A US 4804719 A US4804719 A US 4804719A
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- US
- United States
- Prior art keywords
- sub
- alkyl
- alkoxy
- substituted
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003086 colorant Substances 0.000 title claims abstract description 39
- 229920000728 polyester Polymers 0.000 title abstract description 9
- 229920006149 polyester-amide block copolymer Polymers 0.000 title 1
- -1 hydroxy, carboxy Chemical group 0.000 claims abstract description 81
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000376 reactant Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 103
- 125000003545 alkoxy group Chemical group 0.000 claims description 73
- 125000003118 aryl group Chemical group 0.000 claims description 59
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 55
- 229910052736 halogen Inorganic materials 0.000 claims description 46
- 150000002367 halogens Chemical class 0.000 claims description 46
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 41
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 32
- 125000004423 acyloxy group Chemical group 0.000 claims description 30
- 125000005236 alkanoylamino group Chemical group 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- 150000002431 hydrogen Chemical group 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 23
- 125000004414 alkyl thio group Chemical group 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- 125000003282 alkyl amino group Chemical group 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 16
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 125000000732 arylene group Chemical group 0.000 claims description 13
- 125000001769 aryl amino group Chemical group 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 8
- 125000005113 hydroxyalkoxy group Chemical group 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- XBNVWXKPFORCRI-UHFFFAOYSA-N 2h-naphtho[2,3-f]quinolin-1-one Chemical class C1=CC=CC2=CC3=C4C(=O)CC=NC4=CC=C3C=C21 XBNVWXKPFORCRI-UHFFFAOYSA-N 0.000 claims description 6
- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical class C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- FQORROGUIFBEFC-UHFFFAOYSA-N OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O Chemical compound OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O FQORROGUIFBEFC-UHFFFAOYSA-N 0.000 claims description 6
- CTSKAPUYEZZYQA-UHFFFAOYSA-N ac1lgnjz Chemical class C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC(=O)NC2=C1 CTSKAPUYEZZYQA-UHFFFAOYSA-N 0.000 claims description 6
- 125000005110 aryl thio group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000003435 aroyl group Chemical group 0.000 claims description 5
- 125000004174 2-benzimidazolyl group Chemical group [H]N1C(*)=NC2=C([H])C([H])=C([H])C([H])=C12 0.000 claims description 4
- HCXJFMDOHDNDCC-UHFFFAOYSA-N 5-$l^{1}-oxidanyl-3,4-dihydropyrrol-2-one Chemical group O=C1CCC(=O)[N]1 HCXJFMDOHDNDCC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 4
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 4
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 claims description 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 4
- 125000005239 aroylamino group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000001671 coumarin Nutrition 0.000 claims description 4
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 235000019239 indanthrene blue RS Nutrition 0.000 claims description 4
- 125000005544 phthalimido group Chemical group 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001589 carboacyl group Chemical group 0.000 claims description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 3
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004509 1,3,4-oxadiazol-2-yl group Chemical group O1C(=NN=C1)* 0.000 claims description 2
- 125000004521 1,3,4-thiadiazol-2-yl group Chemical group S1C(=NN=C1)* 0.000 claims description 2
- FUNJHONCFBDKGW-UHFFFAOYSA-N 1,4-benzoxazin-2-one Chemical class C1=CC=C2OC(=O)C=NC2=C1 FUNJHONCFBDKGW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- ZQCQJALTXDGORV-UHFFFAOYSA-N 22281-18-1 Chemical class C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC3=NC4=CC=CC=C4C(=O)N3C2=C1 ZQCQJALTXDGORV-UHFFFAOYSA-N 0.000 claims description 2
- IFXSPEWBAZHCCC-UHFFFAOYSA-N 7,12-dihydroquinoxalino[2,3-b]phenazine Chemical compound C1=CC=C2N=C(C=C3NC=4C(=CC=CC=4)NC3=C3)C3=NC2=C1 IFXSPEWBAZHCCC-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 244000137850 Marrubium vulgare Species 0.000 claims description 2
- DXNQLZJOTVNBOZ-UHFFFAOYSA-N [O]C(=O)Nc1ccccc1 Chemical group [O]C(=O)Nc1ccccc1 DXNQLZJOTVNBOZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005091 alkenylcarbonylamino group Chemical group 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000005081 alkoxyalkoxyalkyl group Chemical group 0.000 claims description 2
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 2
- 125000005115 alkyl carbamoyl group Chemical group 0.000 claims description 2
- 125000005422 alkyl sulfonamido group Chemical group 0.000 claims description 2
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 2
- 125000005333 aroyloxy group Chemical group 0.000 claims description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- LXARMRGJFVAFPR-UHFFFAOYSA-N benzo[a]phenoxazin-5-one Chemical class C12=CC=CC=C2C(=O)C=C2C1=NC1=CC=CC=C1O2 LXARMRGJFVAFPR-UHFFFAOYSA-N 0.000 claims description 2
- WWXLKPRGAXWHFO-UHFFFAOYSA-N benzo[e]perimidin-7-one Chemical class C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=NC=NC2=C1 WWXLKPRGAXWHFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005026 carboxyaryl group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 125000005191 hydroxyalkylamino group Chemical group 0.000 claims description 2
- HQOPRYVUHZJKAO-UHFFFAOYSA-N naphtho[2,3-b]indolizine-6,11-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1N1C=CC=CC1=C2 HQOPRYVUHZJKAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 150000005109 triphenodioxazines Chemical class 0.000 claims description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 1
- 239000000976 ink Substances 0.000 abstract description 11
- 238000007639 printing Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 229920001279 poly(ester amides) Polymers 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 7
- SBLOWDPNVCEPOU-UHFFFAOYSA-N Cc1c([Na])c(C)c(C(O)=O)c(c1C(O)=O)S(O)(=O)=O Chemical compound Cc1c([Na])c(C)c(C(O)=O)c(c1C(O)=O)S(O)(=O)=O SBLOWDPNVCEPOU-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 241000288748 Chrysochloridae Species 0.000 description 4
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000001062 red colorant Substances 0.000 description 3
- BRDWIEOJOWJCLU-LTGWCKQJSA-N GS-441524 Chemical compound C=1C=C2C(N)=NC=NN2C=1[C@]1(C#N)O[C@H](CO)[C@@H](O)[C@H]1O BRDWIEOJOWJCLU-LTGWCKQJSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 239000000038 blue colorant Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- PYAXMGCRUJSCPE-UHFFFAOYSA-N 10h-naphtho[3,2-e][2,1]benzothiazol-9-one Chemical class C12=CSN=C2C=CC2=C1C=C1CC(=O)C=CC1=C2 PYAXMGCRUJSCPE-UHFFFAOYSA-N 0.000 description 1
- OWBMYSRIDBTWEC-UHFFFAOYSA-N 3-[(9,10-dioxoanthracen-1-yl)amino]cyclohexa-1,5-diene-1,3-dicarboxylic acid Chemical compound C1C=CC(C(=O)O)=CC1(C(O)=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O OWBMYSRIDBTWEC-UHFFFAOYSA-N 0.000 description 1
- RVBXFOZIRRHESC-UHFFFAOYSA-N 4h-naphtho[2,3-f]quinazolin-1-one Chemical class C1=CC=CC2=CC3=C4C(=O)NC=NC4=CC=C3C=C21 RVBXFOZIRRHESC-UHFFFAOYSA-N 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000018999 crinkle Diseases 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002183 isoquinolinyl group Chemical class C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical class C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
Definitions
- R 3 represents hydrogen or 1-3 substituents independently selected from alkyl, alkoxy, cyano, alkanoylamino, halogen, and alkylthio;
- R and R' are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, or arylthio; n is 0, 1 or 2;
- R 3 is alkylene, arylene, aralkylene, or alkyleneoxyalkylene
- the water-dispersible polymeric material comprises (a) an acid component (moiety) of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodio-sulfoisophthalic acid, (c) a glycol component (moiety) of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and (e) from about 0.5 to about 10 mole % of mono- or difunctional colorant material; with regard to the polymer, the term "moiety" as used herein designates the residual portion, for example, of the reactant acid or glycol or condensable derivative thereof which actually enters into or onto the polymer chain during the condensation or polycondensation reaction;
Abstract
Water-dispersible polymeric material such as polyesters and poly(ester-amides) containing water-solubilizing sulfonate groups and having reacted onto or into the polymer backbone from about 0.01 to about 40 mol % based on the total of all reactant hydroxy, carboxy or amino equivalents, of colorant comprising one or more heat stable organic compounds initially having one or more condensable groups, the polymeric material comprising the reaction residues of organic monomers and said colorant compounds containing one or more reactive groups condensable under polymerization conditions. This material is useful, for example, for printing inks or other coatings which are desireably applied from an aqueous system.
Description
This invention concerns certain water-dissipatable, water soluble, water dispersible, or water suspensible polymers, all hereinafter termed water-dispersible, containing colorants as an integral part of the polymer structures. The polymers which are thus colored are useful in adhesives, coating materials, films, packaging materials, and products which can be dissolved or otherwise dispersed in cold or hot water. Aqueous dispersions of the colored polymers have utility as inks, paints, and other coatings where it is advantageous to use aqueous as opposed to organic solvents.
The descriptions and manufacture of exemplary base polymer compositions useful herein are given in U.S. Pat. Nos. 3,734,874, 3,779,993, 3,828,010, 4,233,196, and 3,546,008, the disclosures of which are incorporated herein by reference. These base polymers are modified according to the present invention which is defined in its broad sense as water-dispersible polymeric material having linking groups comprising at least about 20 mole % carbonyloxy and up to about 80 mole % carbonylamido, said material containing water-solubilizing sulfonate groups and having reacted onto or into the polymer backbone from about 0.01 to about 40 mol % based on the total of all reactant hydroxy, carboxy or amino equivalents, of colorant comprising one or more heat stable organic compounds initially having at least one condensable group. The aforementioned equivalents encompass the various condensable derivatives thereof including carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl)2 carbamyloxy, alkylamino, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy.
In a highly preferred embodiment of the present invention, the polymeric material contains carbonyloxy linking groups in the linear molecular structure wherein up to 80% of said linking groups may be carbonylamido linking groups, the polymer having an inherent viscosity of from about 0.1 to about 1.0 measured to a 60/40 parts by weight solution of phenol/tetrachloroethane at 25° C. and at a concentration of 0.25 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction residues of the following reactants (a), (b), (c), (d), and (e) or the ester forming or esteramide forming derivatives thereof;
(a) at least one difunctional dicarboxylic acid;
(b) from about 4 to about 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole percent, of at least one difunctional sulfomonomer containing at least one cationic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino;
(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --CH2 --OH groups of which
(1) at least 10 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula:
H--OCH.sub.2 --CH.sub.2 --.sub.n OH,
n being an integer of from 2 to about 20, or
(2) of which from about 0.1 to less than about 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula:
H--OCH.sub.2 --CH.sub.2 --.sub.n OH,
n being an integer of between 2 and about 500, and with the proviso that the mole percent of said poly(ethlene glycol) within said range is inversely proportional to the quantity of n with said range;
(d) from none to at least one difunctional reactant selected from a hydroxycarboxylic acid having one --(C(R)2 --OH group, an amino-carboxylic acid having one --NRH group, and an amino-alcohol having one --C(R)2 --OH group and one --NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) or (d) reactants is a H atom or an alkyl group of 1 to 4 carbon atoms; and
(e) from about 0.1 mole % to about 15 mole %, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole % of colorant having at least one acid, hydroxy or amino group reacted onto or into the polymer chain.
In the above polymeric material it is preferred that very minor, e.g., less than about 10 mol % based on all reactants, of reactant (d) is employed, that at least about 70 mol % of reactant (c) is glycol, and that at least about 70 mol % of all hydroxy equivalents is present in the glycol.
Colorants capable of withstanding the conditions of polymerization and which in varying degrees are useful in the present invention are disclosed, for example, in U.S. Pat. Nos. 4,267,306; 4,359,570; 4,403,092; 4,617,373; 4,617,374; 3,278,486; 3,359,230; 3,401,192; 3,417,048; 3,424,708; 4,088,650; 4,116,923; 4,141,881; 4,477,635; 4,231,918; 3,104,233; 4,202,814; 4,279,802; 4,292,232; 4,344,767; 2,571,319; 3,034,920; 3,489,713; and 3,372,138, the disclosure of which are incorporated herein by reference. Particularly suitable of the above anthraquinone type colorants are those of U.S. Pat Nos. 4,359,570; 4,267,306; and 4,403,092. These colorants include the carboxy, hydroxy, ester, acid halides, and amino derivatives of such types of compounds as anthraquinones; methines; bis-methines, 3H-dibenz[f,ij]isoquinoline 2,7-diones (anthrapyridones); triphenodioxzines; fluorindines; phthaloylpyrrocolines; coumarins; phthaloylacridones; 4-amino-1,8-naphthalimides; thioxanthones; 2,5-arylaminoterephthalic acids (or esters); benzanthrones; 3,6-diaminopyromellitic acid dimides; quinophthalones; naphthalene 1:4:5:8-tetra carboxylic bis-imides; isothiazoloanthrones; anthrapyrimidines; anthrapyrimidones; and indanthrones. A variety of shades, e.g., from yellow to blue can be obtained by either mixing the colorants during polymerization, or by mixing the polymeric compositions containing individual colorants.
Preferred colorant types having excellent stability (good color yield and little, if any, shift in color) include the following: methines; anthraquinones; 3H-dibenz[f,ij]isoquinoline-2,7-diones (anthrapyridones); benzo[f]pyrido[1,2-a]indole-6,11-diones; thioxanthene-9-ones; coumarins; 2H-1,4-benzoxazine-2-ones, triphenodioxazines, 5,12-dihydroquinoxalino[2,3-b]phenazine (fluorindines); 3,6-diaminopyromellitic acid diimides; 2,5(3)diarylaminoterephthalic acids (esters); 4-amino-1,8-naphthalimides; naphtho [1',2',3':4,5]quino[2,1-b]quinazoline-5,10-diones; 7H benzo[de]anthracen-7-ones (benzanthrones); 7H-benzo[e]perimidin-7-ones; 6,15-dihydro-5,9,14,18-anthrazinetetrones (indanthrones); quinophthalones; 7H-benzimidazo[2,1-a][de]isoquinolin-7-ones; 5H-benzo[a]phenoxazine-5-ones; 6H,13H-pyrido[1,2-a: 3,4-b]diindole-6,13-diones; and diindolo [3,2,1-de-3',2',1'-ij][1,5]naphthyridine-6,13-diones.
The anthrapyridones (isoquinoline derivatives or substituted 3H-dibenzo[f,ij]Isoquinoline-2,7-diones) of the general formula (I), for examples, shown below, show excellent thermal stability where R, R2, R3, R4, Z and Z' are selected from hydrogen or, for example, a wide range of substituents including those shown in Table 18 below, giving colors including yellow, orange, red, and blue.
Exemplary anthrapyridones have the formula ##STR1## wherein: R is hydrogen, cycloalkyl or alkyl; X is --O--, --S--, or --NH--; --X--R1 --Z in combination is hydrogen or halogen; R1 is selected from -alkylene-Z', -arylene-Z', -cycloalkylene-Z', -aralkylene-Z', -cycloalkylenealkylene-Z', -alkarylene-Z', -alkylenecycloalkylenealkylene-Z', -alkylenearalkylene-Z', or alkylenecycloalkylene-Z',
wherein --Z and Z' are independently selected from hydrogen, --SO2 R5, --SO2 NR5 R5, --NHSO2 R5, --N(R5)SO2 R5, --N(R5)COR5, --NHCOR5, --OH, --SR5, --OR5, --NHR5, --NR5 R5, --SO2 NHR5, --CONHR5, --CONR5 R5, --CO2 R5, --OCOR5, --OCO2 R5, --OOCNHR5, ##STR2## wherein R5 is hydrogen, alkyl, allyl, aryl, cycloalkyl, hydroxyalkyl, alkoxyalkoxyalkyl, alkoxyalkyl, hydroxyalkoxy, hydroxyalkoxyalkoxy, alkoxycarbonylalkyl or carboxyaryl, and when X is --O--, or --NH--, --R1 --Z in combination also can be hydrogen, R2 is hydrogen, alkyl, aryl, cyano, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, cycloalkylalkoxycarbonyl, COCl, carboxy, carbamyl, N-alkylcarbamyl, N,N-dialkylcarbamyl, N-alkyl-N-arylcarbamyl, N-arylcarbamyl, N-cycloalkylcarbamyl, acyl, aroyl, amino, alkylamino, dialkylamino, arylamino, cycloalkylamino, alkoxy, hydroxy, alkylthio or arylthio; each of R3 and R4 is hydrogen, alkyl, halogen or alkoxy; wherein each of the above alkyl, alkylene, aryl, arylene, cycloalkyl or cycloalkylene moieties or portions of a group or radical may be substituted where appropriate with 1-3 substituents selected from hydroxyl, acyloxy, alkyl, cyano, carboxy, alkoxycarbonyl, alkoxycarbonyloxy, halogen, alkoxy, hydroxyalkoxy, hydroxyalkyl, aryl, aryloxy, or cycloalkyl; and wherein, when the above hydroxyl substituent is absent or multicondensable groups are desired, at least one of R, R2, R3, or R4 carries one or more condensable groups.
In particularly preferred embodiments of the invention: X is --NH-- and --R1 --Z is combination is aryl, aryl substituted with 1-3 of alkyl, alkoxy, halogen, hydroxyalkyl, hydroxyalkoxy or acylamido, alkyl, or alkyl substituted with 1-3 of hydroxyl or acyloxy, cycloalkyl or cycloalkyl substituted with 1-3 of alkyl; --X--R1 --Z in combination is H; R is alkyl; R2 is alkoxycarbonyl, hydroxyalkylamino, or cyano; and R3 and R4 are each hydrogen.
In all of the above definitions the alkyl or alkylene moieties or portions of the various groups contain from 1-8 carbons, straight or branched chain, the aryl or arylene nuclei contain from 4-10 carbons, and the cycloalkyl or cycloalkylene nuclei contain from 4-6 carbons. The suffix "ene," is used herein to designate a divalent radical or group, and the term "cycloalkyl" may be used interchangeably with "cycloaliphatic.".
The present colorant/polymer compositions give stable aqueous dispersions, showing no settling or sludging-out of the colorant. Since the colorants are copolymerized, they cannot be removed from the polymer by extraction or by contact with the body thus minimizing toxicological concerns as regards exposure to organic materials. The invention allows the preparation of aqueous solutions of colored polymer having high tinctorial value and good color stability to change in pH, temperature, concentration and the like.
Further preferred structure types given by exemplary formulae below generally exhibit very acceptable thermal stability. These basic structures are modified as necessary by incorporation of known reactive groups such as --COOH, --OH, ester, or the like. In these formulae, each available position on each ring may be unsubstituted or substituted with an R substituent as defined above. ##STR3## wherein X is, for example, --NHC6 H5, and Y is --NO2 or NHCOCH3, ##STR4## wherein the various R, X, and Y substitutents are as defined above.
Exemplary specific colorants are given below. ##STR5##
Other such useful colorants include those of the general formulae, ##STR6## wherein each Y1 is --NH-- or --S-- and each R represents 0-3 substituents as defined above. In these formulae, the --COOH substituents include the various esters thereof.
Preferred general chemical structures of colorants are given in formulas I, II, III, and IV below. See, for example, U.S. Pat. Nos. 4,403,092; 4,359,570; and 4,267,306. ##STR7## wherein: R1 and R2 each represents hydrogen or 1-3 substituents, depending on the number of T substituents present as defined below, said R1 and R2 being independently selected from alkyl, alkoxy, alkylamino, alkylsulfonyl, alkylsulfonylamino, alkanoylamino, aroylamino, alkylthio, arylamino, amino, cycloalkylamino, alkanoyl, aroyl, arylsulfonyl, CF3, arylsulfamoyl, cyano, halogen, hydroxy, nitro, sulfamoyl, alkylsulfamoyl, dialkylsulfamoyl, carbamoyl, alkylcarbamoyl and dialkylcarbamoyl; and R is 1-4 independently selected substituents of the formula ##STR8## in any positions on rings A and/or B, wherein:
each Z is a divalent linking group independently selected from --NH--, --S--, --O--, --NHR--, --SR--, --SRS--, --SRO--, --SRSR--, --NHRO--, --NHRORO--, --NHRS--, --NHRSR--, --NHRN(COR)--, --NHRN(SO2 R)--, --ORO--, --OR--, --OROR--, --ORORO--, --ORSR--, and --ORN(COR)RO--, wherein R is aralkylene, alkylene, arylene or cycloalkylene;
R3 represents hydrogen or 1-3 substituents independently selected from alkyl, alkoxy, cyano, alkanoylamino, halogen, and alkylthio;
each R4 is independently selected from hydrogen, alkyl, cycloalkyl, and aryl;
each R5 is independently selected from alkylene, arylene, cycloalkylene, arylenealkylene, aryleneoxyalkylene, arylenethioalkylene, alkylenethioalkylene, alkyleneoxyalkylene, arylenedialkylene, and cyclohexylenedialkylene;
Q represents 1-3 groups independently selected from acyloxy, --OCOO-alkyl, hydroxy, carboxy, --COO-alkyl, --COO-aryl, and --COO-cycloalkyl;
and wherein the alkyl, alkylene, cycloalkyl, cycloalkylene, aryl and arylene moieties or segments of the above R1 -R5 groups are unsubstituted or substituted with 1-3 of the following: hydroxy; halogen; cyano; amino; alkoxy; alkoxycarbonyl; aroyloxy; alkoxyalkoxy; hydroxyalkoxy; succinimido; glutarimido; phthalimido; phthalimidino; 2-pyrolidono; cyclohexyl; phenoxy; phenyl; phenyl substituted with alkyl, alkoxy, alkoxycarbonyl, halogen, alkanoylamino or cyano; acrylamido; alkenyl; benzoylsulfonicimido; groups of the formula ##STR9## wherein Y is --NH--, ##STR10## --O--, --S--, >CHOH, or --CH2 --O--; --S--R6 wherein R6 is selected from alkyl, alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, phenyl, phenyl substituted with one or more of halogen, alkyl, alkoxy, alkanoylamino, cyano or alkoxycarbonyl, pyridyl, pyrimidinyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzothiazolyl or ##STR11## --SO2 R8 ; --COOR8 ; --OXR8 ; --NH--X--R8 ;
--CONR7 R7 ; --SO2 NR7 R7 ; wherein X is --CO--, COO--, or --SO2 ; R8 is selected from alkyl, aryl, cycloalkyl, and each of these groups unsubstituted or substituted with 1-3 substituents independently selected from halogen, hydroxy, phenoxy, aryl, alkyl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R8 is further selected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino and furyl; R7 is selected from hydrogen, alkyl, aryl, alkoxysubstituted aryl, cycloalkyl, amino, alkylamino, dialkylamino, arylamino, furyl, and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; alkoxy substituted with 1-3 of hydroxy, cyano or alkanoyloxy; alkoxyalkoxy substituted with 1-3 of hydroxy, cyano, alkanoyloxy or alkoxy; and phenoxy substituted with 1-3 of alkyl, alkoxy or halogen; ##STR12## wherein either or both of rings A and B may contain in any position thereon one or two groups of the formula ##STR13## wherein:
R and R3 each is selected from hydrogen, lower alkyl or hydroxy substituted lower alkyl;
R1, R2, R4 and R5 each represents hydrogen or 1-3 substituents selected from lower alkyl, lower alkyl substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, lower alkoxy, lower alkoxy substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, chlorine, bromine, amino, lower alkylamino, lower alkylamino substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower alkylsulfonyl, lower alkylthio, lower alkanoylamino, or cyclohexylamino;
and wherein each aforesaid aryl moiety is 6-10 carbons; X is --S-- or --NH--; n is 1 or 2; m is 0, 1, or 2. ##STR14## wherein R is --OH, --COOR1 or --COX wherein R1 is --H or lower alkyl, and X is halogen, either of rings A or B may contain one or more groups of the formula ##STR15## wherein R is as defined above, and each of rings A and B may be further substituted with 1-3 substituents selected from: lower alkyl which may be substituted with lower alkoxy, aryl, Cl, Br, or lower alkanoylamino; lower alkoxy which may be substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino; chlorine; bromine; amino; lower alkyl amino which may be substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower alkanoylamino; aryl amino; arylthio; or aroylamino; lower alkylsulfonyl; lower alkylthio; lower alkanoylamino; or cyclohexylamino; wherein each aryl is 6-10 carbons. ##STR16## wherein each A is selected from the following radicals: ##STR17## wherein:
R and R' are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, or arylthio; n is 0, 1 or 2;
R1 and R2 are each selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two of alkyl, --OH, alkoxy, halogen, or hydroxy substituted alkyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, carboxy, cyano, or alkoxycarbonyl; straight or branched lower alkenyl; straight or branched alkyl of 1-8 carbons and such alkyl substituted with the following: hydroxy; halogen; cyano; succinimido; hydroxysuccinimido; acyloxysuccinimido; glutarimido; phenylcarbamoyloxy; phthalimido; 4-carboxyphthalimido; phthalimidino; 2-pyrrolidono; cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; sulfamyl; benzoylsulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula ##STR18## wherein Y is --NH--, ##STR19## --O--, --S--, or --CH2 O--; --S--R14 ; SO2 CH2 CH2 SR14 ; wherein R14 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl; pyridyl; pyrimidinyl; benzoxazolyl; benzimidazolyl; benzothiazolyl; radicals of the formula ##STR20## --OXR16 ; --NHXR16 ; --X--R16 ; --CONR15 R15 ; and --SO2 NR15 R15 ; wherein R15 is selected from H, aryl, alkyl, and alkyl substituted with halogen, --OH, phenoxy, aryl, --CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; X is --CO--, --COO--, or --SO2 --; R16 is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy; and when X is --CO--, R16 also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbalkoxy, or halogen; R1 and R2 can be a single combined group such as pentamethylene, tetramethylene, ethyleneoxyethylene, ethylene sulfonylethylene, or ##STR21##
which, with the nitrogen to which it is attached, forms a ring and wherein R17 is alkyl, aryl, or cycloalkyl;
R3 is alkylene, arylene, aralkylene, or alkyleneoxyalkylene;
Z is selected from a direct single bond, --OCO--, --O--, --S--, --SO2 --, R17 SO2 N═, ##STR22## arylene, or alkylene;
R4, R5, and R6 are each selected from hydrogen or alkyl;
R7 is carboxy, carbalkoxy, or (R)n ;
R10 is hydrogen, alkyl, or aryl;
R8 and R9 are each selected from hydrogen and substituted or unsubstituted alkyl, aryl, or cycloalkyl
R11 and R12 are each selected from hydrogen, alkyl, hydroxyl, or acyloxy;
B represents the atoms necessary to complete a five- or six-membered ring and is selected from ##STR23##
each P and Q is selected from cyano, carbalkenyloxy, carbcycloalkyloxy, carbalkoxy, carbaryloxy, carbaralkyloxy, carbamyl, carboxy, N-alkylcarbamyl, N-alkyl-N-arylcarbamyl, N,N-dialkylcarbamyl,N-arylcarbamyl, N-cyclohexylcarbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, napthyl, pyridyl, pyrimidinyl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl, SO2 alkyl, SO2 aryl, and acyl, or P and Q may be combined as ##STR24##
wherein R17 is defined above and R18 is CN, COOH, CO2 alkyl, carbamyl, or N-alkylcarbamyl;
wherein at least one of A, P, and Q for each dye molecule must be or bear a condensable group selected from carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl)2 carbamyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, or carbocyclohexyloxy;
wherein when an (R) substituent is present, n is any integer up to the available substitution sites on the ring; and
wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted where appropriate with hydroxyl, acyloxy, alkyl, cyano, alkoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl.
In further preferred embodiments of the invention:
(A) the water-dispersible polymeric material comprises (a) an acid component (moiety) of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodio-sulfoisophthalic acid, (c) a glycol component (moiety) of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and (e) from about 0.5 to about 10 mole % of mono- or difunctional colorant material; with regard to the polymer, the term "moiety" as used herein designates the residual portion, for example, of the reactant acid or glycol or condensable derivative thereof which actually enters into or onto the polymer chain during the condensation or polycondensation reaction;
(B) the inherent viscosity of the water-dispersible polymeric material is from about 0.20 to about 0.38, the said acid component (moiety) comprises from about 80 to about 83 mole % isophthalic acid and conversely from about 20 to about 17 mole % 5-sodiosulfoisophthalic acid, and the said glycol component (moiety) comprises from about 52 to about 56 mole % diethylene glycol and conversely from about 48 to about 44 mole % 1,4-cyclohexanedimethanol;
(C) the polyester materials have an inherent viscosity of from about 0.28 to about 0.38, an acid moiety of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodiosulfoisophthalic acid, and a glycol moiety of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 44 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof; and
(C) the acid moiety comprises from about 80 to about 83 mole % isophthalic acid and conversely from about 20 to about 17 mole % 5-sodiosulfoisophthalic acid, and said glycol moiety comprises from about 52 to about 56 mole % diethylene glycol and conversely from about 48 to about 44 mole % 1,4-cyclohexanedimethanol.
The inherent viscosities (I.V.) of the particular polyester materials useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857-70 procedure, in a Wagner Viscometer of Lab Glass, Inc. of Vineland N.J., having a 1/2 mL capillary bulb, using a polymer concentration about 0.25% by weight in 60/40 by weight of phenol/tetrachloroethane. The procedure is carried out by heating the polymer/solvent system at 120° C. for 15 minutes, cooling the solution to 25° C. and measuring the time of flow at 25° C. The I.V. is calculated from the equation: ##EQU1## wherein: (n)=inherent viscosity at 25° C. at a polymer concentration of 0.25 g/100 mL of solvent;
1n=natural logarithm;
ts =sample flow time;
to =solvent-blank flow time; and
C=concentration of polymer in grams per 100 mL of solvent=0.25.
The units of the inherent viscosity throughout this application are in deciliters/gram. It is noted that higher concentrations of polymer, e.g., 0.50 g of polymer/100 mL solvent may be employed for more precise I.V. determinations.
In general, for one particular utility of the present invention, the present colored water-dispersible polyester materials are excellent film formers for water-based printing inks. The polymers form stable solutions or dispersions in water and produce tough, flexible films on drying. Films will form at temperatures down to just above the freezing point of water. The polymers in dispersion form may be plasticized if necessary, for example, with certain water-immiscible phthalate esters to high degrees of flexibility. Printing inks prepared from the present concentrates are readily further water reducible (dilution) and the finished or press-ready inks typically comprise in % by weight, from about 55% to about 90% water, preferably from about 65% to about 75%, and from about 4% to about 30% colored, water-dispersible polymeric material, preferably from about 10% to about 25%, from about 1% to about 20% pigment, preferably from about 8% to about 15%. Various types of modifiers may be used such as up to about 10.0% polyvinyl alcohol or the like. The inks dry rapidly upon printing, wet surfaces exceptionally well and have excellent adhesion to many plastic films and metal foil as well as to paper, glass, polyethylene and many other substrates. Both the 100% solids, water-dissipatable polymers and the corresponding aqueous dispersions thereof may be further pigmented by conventional techniques.
The aforedescribed colored polyester material is prepared according to the polyester preparation technology described in U.S. Pat. Nos. 3,734,874; 3,779,993; and 4,233,196, the disclosures of which are incorporated herein by reference, and the use of the term "acid" in the above description and in the appended claims includes the various ester forming or condensable derivatives of the acid reactants such as the acid halides and dimethyl esters as employed in the preparations set out in these patents. Among the preferred sulfo-monomers are those wherein the sulfonate group is attached to an aromatic nucleus such as benzene, naphthalene, diphenyl, or the like, or wherein the nucleus is cycloaliphatic such as in 1,4-cyclohexanedicarboxylic acid.
Dispersal of the present polyester material in water may be done, for example, at preheated water temperature of about a 180° to about 200° F. and the polymer added as pellets to the vortex under high shear stirring. A Cowles Dissolver, Waring Blender, or similar equipment may be used. Once water is heated to temperature, additional heat input is not required. Depending upon the volume prepared, dispersal of the pellets by stirring should be complete within 15 to 30 minutes. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to nonvolatile levels of about 25%-30%, but generally increase sharply above these levels. Viscosities of the dispersions will be influenced by the degree of polymer dispersion (fineness) obtained which is affected by the dispersing temperature, shear, and time.
Components (a)-(g) comprising
(a) 79.54 g (0.41 m) dimethyl terephthalate,
(b) 26.64 g (0.09 m) dimethyl-5-sodiosulfoisophthalate,
(c) 54.06 g (0.51 m) diethylene glycol,
(d) 37.44 g (0.26 m) 1,4-cyclohexane dimethanol,
(e) 0.74 g (0.009 m) anhydrous sodium acetate,
(f) 100 ppm Ti catalyst as titanium-tetraisopropoxide, and
(g) 0.68 g (1.42×10-3 m) red colorant (1,5-biscarboxyanilinoanthraquinone) ##STR25## were added to a 500-mL round bottom flask that was fitted with a stirrer, condensate take off, and nitrogen inlet head. The flask and contents were immersed into a Belmont metal bath and heated for two hours at about 200°-220° C., while ester interchange and reaction of the colorant with ethylene glycol occurred. To carry out the polycondensation reaction, the temperature was increased to ˜250° C. and the flask was held under vacuum of ≦0.5 mm Hg for about 45 minutes. The resulting polymer was dark red and had an I.V. of 0.323 and Tg=60.0° C. This polymer contains about 0.5% (wt/wt) red colorant, and is readily soluble in hot water producing a dark red aqueous solution.
The procedure of Example 1 was repeated using 2.77 g (4.789×10-3 m) of colorant (g), thus producing a polymer containing about 2.0% (wt/wt) of red colorant and having an I.V. of 0.270 and Tg=58.6° C.
The procedure of Example 1 was repeated using 2.77 g (5.653×10-3 m) of the blue colorant (h) below to produce a dark blue polymer having an I.V. of 0.274 and Tg=62.9° C. ##STR26## The polymer contains about 2.0% (wt/wt) of colorant and gives a dark blue solution in water at room temperature.
The procedure of Example 1 was repeated using 13.59 g (0.028 m) of the blue colorant (h) to give a polymer containing about 10% (wt/wt) of colorant and having an I.V. of 0.286 and Tg=64.6° C.
All four of the above exemplary polymers were easily dissolved in hot water at the 25% solids level to produce stable solutions.
Polyesters designated (a), (b), (c) and (d) may be prepared essentially in accordance with Example 1 of the aforementioned U.S. Pat. No. 4,233,196 from the following materials and including the condensable colorant of choice in molar proportions such as employed in any of Examples 1-4 above.
______________________________________
(a) g. moles
______________________________________
Dimethyl Isophthalate (IPA)
0.415
Dimethyl-5-Sodiosulfoisophthalate (SIP)
0.085
1,4-Cyclohexanedimethanol (CHDM)
0.520
Carbowax 1000 (CW 1000) 0.0237
Sodium Acetate 0.0085
Irganox 1010 0.0085
______________________________________
The Carbowax 1000 has the structure H--OCH2 --CH2 --n OH wherein n is about 22. The polymer should analyze by NMR to contain (in reacted form) about 83 mole % IPA, about 17 Mole % SIP, about 94.5 mole % CHDM, and about 5.5 mole % of CW 1000, and have an I.V. of about 0.39.
______________________________________
(b) g. moles
______________________________________
Dimethyl Isophthalate 0.328
Dimethyl-5-Sodiosulfoisophthalate
0.072
1,4-Cyclohexanedimethanol
0.442
Carbowax 400 (n = 10) 0.058
Sodium Acetate 0.0072
______________________________________
The polymer should analyze by NMR to contain (in reacted form) about 82 mole % IPA, about 18 mole % SIP, about 85.5 mole % CHDM and about 14.5 mole % CW 400, and have an I.V. of about 0.46.
______________________________________
(c) g. moles
______________________________________
Dimethyl Isophthalate 0.41
Dimethyl-5-Sodiosulfoisophthalate
0.09
1,4-Cyclohexanedimethanol
0.55
Carbowax 4000 (n = 90)
0.0005
Sodium Acetate 0.009
______________________________________
The polymer should analyze by NMR to contain (in reacted from) about 82 mole % IPA, about 18 mole % SIP, about 99.9 mole % CHDM and about 0.1 mole % CW 4000, and have an I.V. of about 0.16
______________________________________
(d) g. moles
______________________________________
Dimethyl Isophthalate 0.205
Dimethyl-5-Sodiosulfoisophthalate
0.045
Ethylene Glycol (EG) 0.9638
Carbowax 2000 (n = 45)
0.03625
Sodium Acetate 0.0045
______________________________________
The polymer should analyze by NMR to contain (in reacted from) about 82 mole % IPA, about 18 mole % SIP, about 85.5 mole % EG and about 14.5 mole % CW 2000, and have an I.V. of about 0.34.
In such polymers containing the Carbowax material, the n value is preferably between about 6 and 150.
In accordance with the present invention, inks prepared from the present colored polymers, with or without various property modifiers such as polyvinyl alcohol, Pluronics® or the like would have unexpectedly superior properties such as flow-out or printability, pigment wetting (where pigment is employed as co-colorant), temperature stability (heat and freeze-thaw), nonsettling for extended periods of time, nonpolluting with respect to odor and volatile organics, nonflocculating, wide viscosity, range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, resistance to grease, water and scuff, compatibility with other water-based inks, wet rub resistance, ink mileage characteristics (considerable water dilution allowable at the press), ink press stability in general, printability (clean, sharp transfer without "stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, solvent resistance, alkali, chemical and detergent resistance, blocking resistance, lightfastness, toughness, substrate wetting, hold-out, dry-rate, and no offset on the printing press (coating, e.g., on tension rollers).
The following tables give exemplary colorant reactants useful in the present invention.
TABLE 1
__________________________________________________________________________
##STR27##
(R).sub.n
R.sub.1 R.sub.2 P, Q
__________________________________________________________________________
H CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
CN, CN
H CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
CN, SO.sub.2 CH.sub.3
3-CH.sub.3
CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
CN, CONHC.sub.6 H.sub.5
3-CH.sub.3
CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
CN, SO.sub.2 CH.sub.3
H CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
CN, COC.sub.6 H.sub.5
H CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
##STR28##
3-CH.sub.3
CH.sub.2 CH(OH)CH.sub.3
C.sub.2 H.sub.5
CN, CO.sub.2 CH.sub.3
2,5-di-OCH.sub.3
CH.sub.2 CH(OH)CH.sub.2 OH
C.sub.2 H.sub.5
CN, CONH.sub.2
2-OCH.sub.3, 5-CH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 C.sub.2 H.sub.5
2-OCH.sub.3, 5-Cl
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 C.sub.6 H.sub.5
2-SCH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 C.sub.6 H.sub.11
2-OC.sub.6 H.sub.5
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CONHC.sub.2 H.sub.4 OH
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5
##STR29##
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
##STR30##
(R).sub.n
R.sub.1
R.sub.3 Z P, Q
__________________________________________________________________________
H C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
SO.sub.2 CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
SO.sub.2 CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
O CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2 O
CH.sub.2 CH.sub.2
CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub. 2
##STR31## CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2
##STR32## CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
SS CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
##STR33## CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
##STR34## CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
##STR35## CN, CO.sub.2 CH.sub.3
3-CH.sub.3
C.sub.2 H.sub.5
CH.sub.2 CH.sub.2
##STR36##
##STR37##
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
##STR38##
(R).sub.n
R.sub.1 R.sub.4, R.sub.5
R.sub.6
P, Q
__________________________________________________________________________
H C.sub.2 H.sub.5
CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.3
H CH.sub.2 CH.sub.2 OH
CH.sub.3, CH.sub.3
CH.sub.3
CN, SO.sub.2 CH.sub.3
H CH.sub.2 CH.sub.2 OH
CH.sub.3, CH.sub.3
CH.sub.3
CO.sub.2 CH.sub.3, CO.sub.2 CH.sub.3
H CH.sub.2 CH.sub.2 OH
CH.sub.3, CH.sub.3
CH.sub.3
CN, SO.sub.2 C.sub.6 H.sub.5
7-CH.sub.3
CH.sub.2 CH.sub.2 OH
CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 C.sub.2 H.sub.5
7-CH.sub.3
##STR39## CH.sub.3, CH.sub.3
CH.sub.3
CN, CN
7-CH.sub.3
##STR40## CH.sub.3, CH.sub.3
CH.sub.3
CN, CN
7-CH.sub.3
C.sub.2 H.sub.4 CN
CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.3
7-CH.sub.3
C.sub.2 H.sub.4 OH
CH.sub.3, CH.sub.3
CH.sub.3
CN, CONHC.sub.6 H.sub.5
7-CH.sub.3
C.sub.2 H.sub.4 OH
CH.sub.3, CH.sub.3
CH.sub.3
##STR41##
7-CH.sub.3
C.sub.2 H.sub.4 OH
CH.sub.3, CH.sub.3
CH.sub.3
##STR42##
__________________________________________________________________________
TABLE 4
______________________________________
##STR43##
(R).sub.n
R.sub.1 R.sub.4 P, Q
______________________________________
H C.sub.2 H.sub.4 OH
H CN, CN
H C.sub.2 H.sub.4 OH
H CN, SO.sub.2 CH.sub.3
H C.sub.2 H.sub.4 OH
H CN, SO.sub.2 C.sub.6 H.sub.5
H C.sub.2 H.sub.4 OH
H CN, CONHC.sub.6 H.sub.5
H C.sub.2 H.sub.4 OH
H CN, CONHC.sub.2 H.sub.4 OH
##STR44## H CN, CN
H
##STR45## H CN, SO.sub.2 CH.sub. 3
6-CH.sub.3
##STR46## H CN, CO.sub.2 CH.sub.3
6-CH.sub.3
##STR47## 3-CH.sub.3
CN, CO.sub.2 CH.sub.3
6-CH.sub.3
##STR48## 3-CH.sub.3
##STR49##
______________________________________
TABLE 5
______________________________________
##STR50##
R.sub.7
R.sub.1 R.sub.10
P, Q
______________________________________
H CH.sub.3 CH.sub.3
CN, CO.sub.2 CH.sub.3
H CH.sub.3 C.sub.6 H.sub.5
CN, CO.sub.2 CH.sub.3
H H C.sub.6 H.sub.5
CN, CO.sub.2 C.sub.2 H.sub.5
##STR51## C.sub.6 H.sub.5
CN, SO.sub.2 CH.sub.3
H
##STR52## C.sub.6 H.sub.5
CN, SO.sub.2 C.sub.6 H.sub.5
H
##STR53## C.sub.6 H.sub.5
CN, CN
H
##STR54## C.sub.6 H.sub.5
##STR55##
H
##STR56## C.sub.6 H.sub.5
CN, CONHC.sub.6 H.sub.5
H CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
##STR57##
______________________________________
TABLE 6
______________________________________
##STR58##
R.sub.8 R.sub.9 R.sub.10
P, Q
______________________________________
CH.sub.3
CH.sub.3 CH.sub.3
CN, CO.sub.2 CH.sub.3
CH.sub.3
CH.sub.3 CH.sub.3
CN, CO.sub.2 C.sub.2 H.sub.5
CH.sub.3
CH.sub.3 C.sub.6 H.sub.5
CN, CO.sub.2 CH.sub.3
CH.sub.3
CH.sub.3 C.sub.6 H.sub.5
CN, COOH
CH.sub.3
CH.sub.3 C.sub.6 H.sub.5
CO.sub.2 C.sub.2 H.sub.5, CO.sub.2 C.sub.2
H.sub.5
CH.sub.3
CH.sub.3 C.sub.6 H.sub.5
CN, CONHC.sub.2 H.sub.4 OH
CH.sub.3
CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
CN, CN
CH.sub.3
CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
CN, SO.sub.2 CH.sub.3
CH.sub.3
CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
CN, SO.sub.2 C.sub.6 H.sub.5
CH.sub.3
CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
CN, CONHC.sub.6 H.sub.5
CH.sub.3
CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
##STR59##
CH.sub.3
CH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.5
##STR60##
______________________________________
TABLE 7
______________________________________
##STR61##
(R).sub.n
R.sub.11
R.sub.12 P, Q
______________________________________
H H H CN, CO.sub.2 CH.sub.3
H H H CN, CO.sub.2 CH.sub.2 CH.sub.2 CN
H H H CN, CO.sub.2 CH.sub.2 CH.sub.2 OH
H H H CN, CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
H H H CN, CO.sub.2 CH.sub.2 C.sub.6 H.sub.11
H H H CO.sub.2 C.sub.2 H.sub.5, CO.sub.2 C.sub.2
H.sub.5
H H H COOH, CN
H H H
##STR62##
5-CH.sub.3
H H CN, CO.sub.2 CH.sub.3
5-OCH.sub.3
H H CN, CO.sub.2 CH.sub.3
5-Cl H H CN, CO.sub.2 CH.sub.3
5,7-di-CH.sub.3
H H CN, CO.sub.2 CH.sub.3
5-CH.sub.3
OH H CN, CN
______________________________________
TABLE 8 ______________________________________ ##STR63## R.sub.7 P, Q ______________________________________ H CN, CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3, CO.sub.2 CH.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3, SO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3, SO.sub.2 C.sub.6 H.sub.5 H CN, CONHC.sub.2 H.sub.4 OH H CN, CO.sub.2 CH.sub.2 CH.sub.2 OH H CN, CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 H CN, CO.sub.2 CH.sub.2 CH.sub.2 Cl H CN, CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 H CN, CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 H CN, CO.sub.2 C.sub.6 H.sub.5 H CN, CO.sub.2 C.sub.6 H.sub.11 H CN, CO.sub.2 CH.sub.2 C.sub.6 H.sub.11 H CN, CO.sub.2 CH.sub.2 C.sub.6 H.sub.5 5-CH.sub.3 CN, CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 ______________________________________
TABLE 9
__________________________________________________________________________
##STR64##
(R).sub.n R.sub.1 R.sub.2
P, Q
__________________________________________________________________________
H CH.sub.3 CH.sub.3
CN, CO.sub.2 C.sub.2 H.sub.5
H CH.sub.3 CH.sub.3
CN, CO.sub.2 C.sub.2 H.sub.4 OH
3-CH.sub.3
CH.sub.3 CH.sub.3
CN, CO.sub.2 CH.sub.3
3-OC.sub.2 H.sub.5
CH.sub.3 CH.sub.3
CN, CO.sub.2 CH.sub.3
3-Cl CH.sub.3 CH.sub.3
CN, CO.sub.2 CH.sub.2 CH.sub.2 CN
2-OCH.sub.3, 5-CH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3
2,5-di-OCH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 C.sub.6 H.sub.5
2,5-di-CH.sub.3
C.sub.2 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
3-CH.sub.3
C.sub.4 H.sub.9-n
C.sub.4 H.sub.9-n
CN, CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.6
H.sub.5
3-C.sub.2 H.sub.5
CH.sub.2 CH(CH.sub.3).sub.2
C.sub.2 H.sub.5
CN, CONHC.sub.2 H.sub.4 OH
H C.sub.6 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 CH.sub.3
3-OCH.sub.3
C.sub.6 H.sub.5
C.sub.2 H.sub.5
CN, CO.sub.2 CH.sub.3
H C.sub.6 H.sub.5
C.sub.6 H.sub.5
CN, CO.sub.2 CH.sub.3
H C.sub.6 H.sub.5
C.sub.6 H.sub.5
CO.sub.2 C.sub.2 H.sub.5, CO.sub.2 C.sub.2
H.sub.5
H C.sub.6 H.sub.11
C.sub.6 H.sub.11
CN, CO.sub.2 CH.sub.3
__________________________________________________________________________
TABLE 10
__________________________________________________________________________
##STR65##
(R).sub.n
R.sub.1 R.sub.4, R.sub.5
R.sub.6
P, Q
__________________________________________________________________________
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.3
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 C.sub.2 H.sub.4 OH
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CONHC.sub.2 H.sub.4 OH
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.2 CH.sub.2 CN
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.2 C.sub.6 H.sub.5
H CH.sub.3 CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
H CH.sub.2 CH.sub.2 Cl
CH.sub.3, CH.sub.3
CH.sub.3
CN, CO.sub.2 C.sub.2 H.sub.5
H CH.sub.2 CH.sub.2 OH
CH.sub.3, CH.sub.3
CH.sub.3
CO.sub.2 C.sub.2 H.sub.5, CO.sub.2 C.sub.2
H.sub.5
H CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
CH.sub.3, CH.sub.3
CH.sub.3
CO.sub.2 CH.sub.3, SO.sub.2 CH.sub.3
##STR66## CH.sub.3, CH.sub.3
CH.sub.3
CN, CN
H
##STR67## CH.sub.3, CH.sub.3
CH.sub.3
CN, SO.sub.2 C.sub.6 H.sub.5
__________________________________________________________________________
TABLE 11
______________________________________
##STR68##
(R).sub.n
(R').sub.n R.sub.1 P, Q
______________________________________
H H CH.sub.2 CH.sub.2 OH
CH, CN
H H CH.sub.2 CH.sub.2 OH
CN, CONH.sub.2
H H CH.sub.2 CH.sub.2 OH
CN, CO.sub.2 CH.sub.3
H H CH.sub.2 CH.sub.2 OH
CN, CONHC.sub.6 H.sub.5
H H CH.sub.2 CH.sub.2 OH
##STR69##
H H
##STR70## CN, CN
H H
##STR71## CN, CO.sub.2 CH.sub.3
H H
##STR72## CN, SO.sub.2 CH.sub.3
H H
##STR73## CN, SO.sub.2 C.sub.6 H.sub.5
H H H CN, CN
H H CH.sub.2 CH.sub.3
CN, CN
______________________________________
TABLE 12
______________________________________
##STR74##
A (R).sub.n
P
______________________________________
##STR75## H CN
##STR76## H CN
##STR77## H CN
##STR78## H CO.sub.2 CH.sub.3
##STR79## H CO.sub.2 CH.sub.3
##STR80## 2-CH.sub.3
CO.sub.2 CH.sub.3
##STR81## 2-Cl CONH.sub.2
______________________________________
TABLE 13
______________________________________
##STR82##
(R).sub.n R.sub.1 P, Q
______________________________________
H C.sub.2 H.sub.4 OH
CN, CN
H C.sub.2 H.sub.4 OH
CN, SO.sub.2 CH.sub.3
H C.sub.2 H.sub.4 OH
CN, SO.sub.2 C.sub.6 H.sub.5
H C.sub.2 H.sub.4 OH
CN, CONHC.sub.6 H.sub.5
H C.sub.2 H.sub.4 OH
CN, CONHC.sub.2 H.sub.4 OH
##STR83## CN, CN
H
##STR84## CN, SO.sub.2 CH.sub.2
4,8-di-CH.sub.3
##STR85## CN, CO.sub.2 CH.sub.3
8-CH.sub.3
##STR86## CN, CO.sub.2 CH.sub.3
8-CH.sub.3
##STR87##
##STR88##
8-CH.sub.3
CH.sub.2 CH(OH)CH.sub.3
##STR89##
______________________________________
TABLE 14
______________________________________
##STR90##
(R).sub.n
R.sub.1 P, Q
______________________________________
H C.sub.2 H.sub.4 OH CN, CN
H C.sub.2 H.sub.4 OH CN, SO.sub.2 CH.sub.3
##STR91## CN, SO.sub.2 C.sub.6 H.sub.5
H
##STR92## CN, CONHC.sub.6 H.sub.5
H C.sub. 2 H.sub.4 OH CN, CONHC.sub.2 H.sub.4 OH
H
##STR93## CN, CN
H
##STR94## CN, SO.sub.2 CH.sub.3
8-CH.sub.3
##STR95## CN, CO.sub.2 CH.sub.3
8-CH.sub.3
##STR96## CN, CO.sub.2 CH.sub.3
______________________________________
TABLE 15
______________________________________
##STR97##
R.sub.1 R.sub.10 P, Q
______________________________________
##STR98## 3,5-di-CH.sub.3
CN, CN
##STR99## 3,5-di-C.sub.6 H.sub.5
CN, SO.sub.2 CH.sub.3
##STR100## 5-CH.sub.3 CN, SO.sub.2 C.sub.6 H.sub.5
##STR101## 3-CH.sub.3 CN, CONHC.sub. 6 H.sub.5
##STR102## 3-C.sub.6 H.sub.5
CN, CONHC.sub.2 H.sub.4 OH
##STR103## 3-C.sub.6 H.sub.5
CN, CN
##STR104## 3,5-di-C.sub.6 H.sub.4p-CH.sub.3
CN, SO.sub.2 CH.sub.3
______________________________________
TABLE 16
______________________________________
##STR105##
(R).sub.n
R.sub.1 P, Q
______________________________________
H CH.sub.2 CH.sub.2 OH
CN, CN
H CH.sub.2 CH.sub.2 OH
CN, CO.sub.2 CH.sub.3
##STR106##
##STR107##
5-CH.sub.3
CH.sub.3
##STR108##
3-CH.sub.3
H
##STR109##
H CH.sub.2 C.sub.6 H.sub.4p-COOH
##STR110##
______________________________________
TABLE 17
______________________________________
##STR111##
(R).sub.n
R.sub.1 P, Q
______________________________________
2,5-di-CH.sub.3
CH.sub.3 CN, CO.sub.2 CH.sub.3
H H
##STR112##
H CH.sub.2 C.sub.6 H.sub.5
##STR113##
H CH.sub.2 C.sub.6 H.sub.4p-CO.sub.2 CH.sub.3
##STR114##
##STR115##
##STR116##
2,5-di-CH.sub.3
C.sub.6 H.sub.5 CN, CO.sub.2 CH.sub.3
2,5-di-CH.sub.3
C.sub.6 H.sub.4p-COOH
##STR117##
______________________________________
TABLE 18
__________________________________________________________________________
Substituted 3HDibenzo[f,ij]Isoquinoline-2,7-Diones
##STR118##
R XR.sub.1Z R.sub.2 R.sub.4
R.sub.3
__________________________________________________________________________
CH.sub.3
NHC.sub.2 H.sub.4 OH
NC H H
CH.sub.3
##STR119## NC H H
CH.sub.3
##STR120## NC H H
H H NHC.sub.2 H.sub.4 OH
9-Cl
CH.sub.2 CH.sub.2 OH
H NHC.sub.6 H.sub.4m-Cl
9-CH.sub.3
CF.sub.3
CH.sub.3
##STR121## CN H C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH
SC.sub.2 H.sub.4 OH COCH.sub.3
H OC.sub.6 H.sub.5
CH.sub.3
NHC.sub.6 H.sub.4p-CH.sub.2CH.sub.2 OH
COOC.sub.2 H.sub.5
H CN
CH.sub.3
NHC.sub.6 H.sub.4m-CH.sub.2 OH
COCH.sub.3
10-CH.sub.3
OC.sub.2 H.sub.5
CH.sub.3
NHC.sub.6 H.sub.4(o, m or p)-CH.sub.3
COOC.sub.2 H.sub.5
9-OC.sub.2 H.sub.5
SC.sub.2 H.sub.5
CH.sub.3
NHC.sub.6 H.sub.5 COOC.sub.2 H.sub.5
9-NHC.sub.2 H.sub.5
COC.sub.6 H.sub.5
CH.sub.3
NHC.sub.2 H.sub.4 OH
COC.sub.6 H.sub.5
H SC.sub.6 H.sub.5
CH.sub.3
NHC.sub.2 H.sub.4 OH
COOC.sub.2 H.sub.5
H OC.sub.2 H.sub.4 OH
CH.sub.3
##STR122## CN H COCH.sub.3
CH.sub.3
##STR123## CN H SO.sub.2 CH.sub.3
CH.sub.3
##STR124## COOC.sub.2 H.sub.5
H COOCH.sub.3
CH.sub.3
NHC.sub.2 H.sub.4 OH
CN H SO.sub.2 C.sub.6 H.sub.5
CH.sub.3
NHC.sub.6 H.sub.4o-CH.sub.3
CN 9-COOCH.sub.3
CF.sub. 3
CH.sub.3
NHC.sub.6 H.sub.4m-CH.sub.2 OH
CN H CH.sub.3
CH.sub.3
NHC.sub.6 H.sub.4(o, m or p)C.sub.2 H.sub.4 OCOCH.sub.3
CN H OCH.sub.3
__________________________________________________________________________
TABLE 19
______________________________________
##STR125##
Y R
______________________________________
OH 4-CH.sub.3
OH 2-OC.sub.2 H.sub.5
OH 3-CH.sub.3
OH 2,4-di-CH.sub.3
OH 2,5-di-OCH.sub.3
OH 2,5-di-Cl
OH 2,4-di-OC.sub.2 H.sub.5
Cl 4-Cl
OH 3-Br
OH 3-CF.sub.3
OH 4-C.sub.2 H.sub.5
OH 4-SC.sub.4 H.sub.9n
OH 4-OC.sub.6 H.sub.5
OH
##STR126##
OH
##STR127##
______________________________________
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims (15)
1. Composition of matter comprising water-dispersible polymeric material having linking groups comprising at least 20 mole % carbonyloxy and up to about 80 mole % carbonylamido, said material containing water-solubilizing sulfonate groups and having reacted onto or into the polymer backbone from about 0.01 to about 40 mole % based on the total of all reactant hydroxy, carboxy or amino equivalents, or the condensable derivative equivalents thereof, of colorant comprising one or more heat stable organic compounds initially having at least one condensable group.
2. The composition of claim 1, wherein the polymer has an inherent viscosity of from about 0.1 to about 1.0 measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25° C. and at a concentration of 0.25 gram of polymer in 100 mL of the solvent, the polymer containing substantially equimolar proportions of acid equivalents (100 mole percent) to hydroxy and amino equivalents (100 mole percent), the polymer comprising the reaction residues of the following reactants (a), (b), (c), (d), and (e) or the ester forming or esteramide forming derivatives thereof:
(a) at least one difunctional dicarboxylic acid;
(b) from about 4 to about 25 mole percent, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole percent, or at least one difunctional sulfomonomer containing at least one cationic sulfonate group attached to an aromatic or cycloaliphatic nucleus wherein the functional groups are hydroxy, carboxyl or amino;
(c) at least one difunctional reactant selected from a glycol or a mixture of a glycol and diamine having two --NRH groups, the glycol containing two --CH2 --OH groups of which
(1) at least 10 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula:
H--OCH.sub.2 --CH.sub.2 --.sub.n OH,
n being an integer of from 2 to about 20, or
(2) of which from about 0.1 to less than about 15 mole percent, based on the total mole percent of hydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol) having the structural formula:
H--OCH.sub.2 --CH.sub.2 --.sub.n OH,
n being an integer of between 2 and about 500, and with the proviso that the mole percent of said poly(ethlene glycol) within said range is inversely proportional to the quantity of n with said range;
(d) from none to at least one difunctional reactant selected from a hydroxycarboxylic acid having one --C(R)2 --OH group, an amino--carboxylic acid having one --NRH group, and an amino-alcohol having one --C(R)2 --OH group and one --NRH group, or mixtures of said difunctional reactants; wherein each R in the (c) or (d) reactants is a H atom or an alkyl group of 1 to 4 carbon atoms; and
(e) from about 0.1 mole % to about 15 mole %, based on a total of all acid, hydroxyl and amino equivalents being equal to 200 mole % of colorant having at least one acid, hydroxy or amino group reacted onto or into the polymer chain.
3. The composition of claim 2 wherein the polymeric material contains less than about 10 mol %, based on all reactants, of reactant (d), at least about 70 mol % of reactant (c) is glycol, and at least about 70 mol % of all hydroxy equivalents is present in the glycol.
4. The composition of claim 3 wherein the colorant is selected from: anthraquinones; methines; bis-methines; 3H-dibenz[f,ij]isoquinoline 2,7-diones (anthrapyridones); triphenodioxzines; fluoridines; phthaloylpyrrocolines; coumarins; 4-amino-1,8-naphthalimides; thioxanthones; 2,5-arylaminoterephthalic acids (or esters); benzanthrones; and indanthrones; said colorants containing at least one condensable group.
5. The composition of claim 3 wherein the colorant is selected from 3H-dibenz[f,ij]isoquinoline-2,7-diones (anthrapyridones); benzo[f]pyrido[1,2-a]indole-6,11-diones; thioxanthene-9-ones; coumarins; 2H-1,4-benzoxazine-2-ones; triphenodioxazines; 5,12-dihydroquinoxalino[2,3-b]phenazine (fluorindines); 3,6-diaminopyromellitic acid diimides; 2,5(3)diarylaminoterephthalic acids (esters); 4-amino-1,8-naphthalimides; naphtho [1',2',3':4,5]quino[2,1-b]quinazoline-5,10-diones; 7H benzo[de]anthracen-7-ones (benzanthrones); 7H-benzo[e]perimidin-7-ones; 6,15-dihydro-5,9,14,18-anthrazinetetrones (indanthrones); quinophthalones; 7H-benzimidazo[2,1-a][de]isoquinolin-7-ones; 5H-benzo[a]phenoxazine-5-ones; 6H,13H-pyrido[1,2-a: 3,4-b]diindole-6,13-diones; and diindolo[3,2,1-de-3',2',1'-ij][1,5]naphthyridine-6,13-dione.
6. The composition of claim 3 wherein the colorant is selected from those of the formula: ##STR128## wherein: R is hydrogen, cycloalkyl or alkyl; X is --O--, --S--, or --NH--; --X--R1 --Z in combination is hydrogen or halogen; R1 is selected from -alkylene-Z', -arylene-Z', -cycloalkylene-Z', -aralkylene-Z', -cycloalkylenealkylene-Z', -alkarylene-Z', -alkylenecycloalkylenealkylene-Z', -alkylenearalkylene-Z', or alkylenecycloalkylene-Z', wherein -Z and Z' are independently selected from hydrogen, --SO2 R5, --SO2 NR5 R5, --NHSO2 R5, --N(R5)SO2 R5, --N(R5)COR5, --NHCOR5, --OH, --SR5, --OR5, --NHR5, --NR5 R5, --SO2 NHR5, --CONHR5, --CONR5 R5, --CO2 R5, --OCOR5, --OCO2 R5, --OOCNHR5, ##STR129## wherein R5 is hydrogen, alkyl, allyl, aryl, cycloalkyl, hydroxyalkyl, alkoxyalkoxyalkyl, alkoxyalkyl, hydroxyalkoxy, hydroxyalkoxyalkoxy, alkoxycarbonylalkyl or carboxyaryl, and when X is --O--, or --NH--, --R1 --Z in combination also can be hydrogen; R2 is hydrogen, alkyl, aryl, cyano, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, cycloalkylalkoxycarbonyl, COCl, carboxy, carbamyl, N-alkylcarbamyl, N,N-dialkylcarbamyl, N-alkyl-N-arylcarbamyl, N-arylcarbamyl, N-cycloalkylcarbamyl, acyl, aroyl, amino, alkylamino, dialkylamino, arylamino, cycloalkylamino, alkoxy, hydroxy, alkylthio or arylthio; and each of R3 and R4 is hydrogen, alkyl, halogen or alkoxy; wherein each of the above alkyl, alkylene, aryl, arylene, cycloalkyl or cycloalkylene moieties or portions of a group or radical may be substituted with 1-3 substituents selected from hydroxyl, carboxyl, carboxy ester, acyloxy, alkyl, cyano, alkoxycarbonyl, alkoxycarbonyloxy, halogen, alkoxy, hydroxyalkoxy, hydroxyalkyl, aryl, aryloxy, or cycloalkyl.
7. The composition of claim 6 wherein X is --NH-- and --R1 --Z in combination is selected from: aryl; aryl substituted with 1-3 of alkyl, alkoxy, halogen, hydroxyalkyl, hydroxyalkoxy or acylamido; alkyl; alkyl substituted with 1-3 of hydroxyl or acyloxy; cycloalkyl; or cycloalkyl substituted with 1-3 of alkyl; --X--R1 --Z in combination is H; R is alkyl; R2 is alkoxycarbonyl, hydroxyalkylamino, or cyano; and R3 and R4 are each hydrogen.
8. The composition of claim 3 wherein the colorant is selected from those of the formulae ##STR130## wherein Y1 is --NH or --S--, and each R, when present, is selected from Cl, Br, alkyl of 1-10 carbons, aryl, aroyl, cycloalkyl, CN, alkoxy of 1-6 carbons, hydroxyalkyl of 1-6 carbons, alkanoyl of 1-6 carbons, alkoxycarbonyl of 1-6 carbons, alkanoyloxy of 1-6 carbons, alkylamino of 1-6 carbons, alkanoylamino of 1-6 carbons, or mono- or dialkylcarbamyl of 1-6 carbons.
9. The composition of claim 3 wherein the water-dispersible polymeric material comprises (a) an acid component of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodio-sulfoisophthalic acid, (c) a glycol component of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, and (e) from about 0.5 to about 10 mole % of mono- or difunctional colorant.
10. The composition of claim 3 wherein the inherent viscosity of the water-dispersible polymeric material is from about 0.28 to about 0.38, the said acid component comprises from about 80 to about 83 mole % isophthalic acid and conversely from about 20 to about 17 mole % 5-sodiosulfoisophthalic acid, and the said glycol component comprises from about 52 to about 56 mole % diethylene glycol and conversely from about 48 to about 44 mole % 1,4-cyclohexanedimethanol.
11. The composition of claim 8 wherein the polymeric material has an inherent viscosity of from about 0.20 to about 0.38.
12. The composition of matter of claim 1, wherein the colorant comprises one or more compounds of the formula ##STR131## wherein: R1 and R2 each represents hydrogen or 1-3 substituents, depending on the number of T substituents present, and are independently selected from alkyl, alkoxy, alkylamino, alkylsulfonyl, alkylsulfonylamino, alkanoylamino, aroylamino, alkylthio, arylamino, amino, cycloalkylamino, alkanoyl, aroyl, arylsulfonyl, CF3, arylsulfamoyl, cyano, halogen, hydroxy, nitro, sulfamoyl, alkylsulfamoyl, dialkylsulfamoyl, carbamoyl, alkylcarbamoyl and dialkylcarbamoyl; and T is 1-4 independently selected substituents of the formula ##STR132## in any positions on rings A and/or B, wherein: each Z is a divalent linking group independently selected from --NH--, --S--, --O--, --NHR--, --SR--, --SRS--, --SRO--, --SRSR--, --NHRO--, --NHRORO--, --NHRS--, --NHRSR--, --NHRN(COR)--, --NHRN(SO2 R)--, --ORO--, --OR--, --OROR--, --ORORO--, --ORSR--, and --ORN(COR)RO--, wherein R is aralkylene, alkylene, arylene or cycloalkylene;
R3 represents hydrogen or 1-3 substituents independently selected from alkyl, alkoxy, cyano, alkanoylamino, halogen, and alkylthio;
each R4 is independently selected from hydrogen, alkyl, cycloalkyl, and aryl;
each R5 is independently selected from alkylene, arylene, cycloalkylene, arylenealkylene, aryleneoxyalkylene, arylenethioalkylene, alkylenethioalkylene, alkyleneoxyalkylene, arylenedialkylene, and cyclohexylenedialkylene;
each Q represents 1-3 groups independently selected from acyloxy; --OCOO-alkyl, hydroxy, carboxy, --COO-alkyl, --COO-aryl, and --COO-cycloalkyl;
and wherein the alkyl, alkylene, cycloalkyl, cycloalkylene, aryl and arylene moieties or portions of the above R1 -R5 groups are unsubstituted or substituted with 1-3 of the following; hydroxy, halogen; cyano; amino; alkoxy; alkoxycarbonyl; aroyloxy; alkoxyalkoxy; hydroxyalkoxy; succinimido; glutarimido; phthalimido; phthalimidino; 2-pyrolidono; cyclohexyl; phenoxy; phenyl; phenyl substituted with alkyl, alkoxy, alkoxycarbonyl, halogen, alkanoylamino or cyano; acrylamido; alkenyl; benzoylsulfonicimido; groups of the formula ##STR133## wherein Y is --NH--, ##STR134## --O--, --S--, >CHOH, or --CH2 --O--; --S--R6 wherein R6 is selected from alkyl, alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, phenyl, phenyl substituted with one or more of halogen, alkyl, alkoxy, alkanoylamino, cyano or alkoxycarbonyl, pyridyl, pyrimidinyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzothiazolyl or groups of the formula ##STR135## --SO2 R8 ; --COOR8 ; --OXR8 ; --NH--X--R8 ; --CONR7 R7 ; --SO2 NR7 R7 ; wherein X is --CO--, COO--, or --SO2 ; R8 is selected from alkyl, aryl, cycloalkyl, and each of these groups substituted with 1-3 substituents independently selected from halogen, hydroxy, phenoxy, aryl, alkyl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, and when X is --CO--, R8 is further selected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino or furyl; R7 is selected from hydrogen, alkyl, aryl, alkoxysubstituted aryl, cycloalkyl, amino, alkylamino, dialkylamino, arylamino, furyl, or alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; alkoxy substituted with 1-3 of hydroxy, cyano or alkanoyloxy; alkoxyalkoxy substituted with 1-3 of hydroxy, cyano, alkanoyloxy or alkoxy; or phenoxy substituted with 1-3 of alkyl, alkoxy or halogen.
13. The composition of matter of claim 1, wherein the colorant comprises one or more compounds of the formula ##STR136## wherein either or both of rings A and B may contain in any position thereon one or two groups of the formula ##STR137## wherein: R and R3 each is selected from hydrogen, lower alkyl or hydroxy substituted lower alky; R1, R2, R4 and R5 each represents hydrogen or 1-3 substituents selected from lower alkyl, lower alkyl substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, lower alkoxy, lower alkoxy substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino, chlorine, bromine, amino, lower alkylamino, lower alkylamino substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower alkylsulfonyl, lower alkylthio, lower alkanoylamino, or cyclohexylamino; wherein each aforesaid aryl moiety is 6-10 carbons; X is --S-- or --NH--; n is 1 or 2; and m is 0, 1, or 2.
14. The composition of claim 1, wherein the colorant comprises one or more compounds of the formula ##STR138## wherein: R is --OH, --COOR1 or --COX wherein R1 is --H or lower alkyl and X is halogen; either or both of A and B may contain at least one additional group of the formula ##STR139## wherein n is 1 or 2; and wherein each of rings A and B may be further substituted with 1-3 radicals selected from the following: lower alkyl which may be substituted with lower alkoxy, aryl, Cl, Br, or lower alkanoylamino; lower alkoxy which may be substituted with lower alkoxy, phenyl, Cl, Br, or lower alkanoylamino; chlorine; bromine; amino; lower alkyl amino which may be substituted with lower alkoxy, cyclohexyl, phenyl, Cl, Br, or lower alkanoylamino; arylamino, arylthio, or aroylamino, wherein each aryl is 6-10 carbons; lower alkylsulfonyl; lower alkylthio; lower alkanoylamino; or cyclohexylamino.
15. The composition of claim 1, wherein the colorant comprises one or more compounds of the formulae ##STR140## wherein each A is selected from the following radicals: ##STR141## wherein: R and R' are selected from hydrogen, fluorine, chlorine, bromine, alkyl, alkoxy, phenyl, phenoxy, alkylthio, or arylthio; n is 0, 1 or 2;
R1 and R2 are each selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two of alkyl; --OH, alkoxy, halogen, or hydroxy substituted alkyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, carboxy, cyano, or alkoxycarbonyl; straight or branched lower alkenyl; straight or branched alkyl of 1-8 carbons and such alkyl substituted with the following: hydroxy; halogen; cyano; succinimido; hydroxysuccinimido; acyloxysuccinimido; glutarimido; phenylcarbamoyloxy; phthalimido; 4-carboxyphthalimido; phthalimidino; 2-pyrrolidino; cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, hydroxy alkanoylamino, carboxy, cyano, or alkoxycarbonyl; alkylsulfamoyl, vinylsulfonyl; acrylamido; sulfamyl; benzoyl-sulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula ##STR142## wherein Y is --NH--, ##STR143## --O--, --S--, or --CH2 O--; --S--R14 ; SO2 CH2 CH2 SR14 ; wherein R14 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl; pyridyl; pyrimidinyl; benzoxazolyl; benzimidazolyl; benzothiazolyl; radicals of the formula ##STR144## --OXR16 ; --NHXR16 ; --X--R16 ; --CONR15 R15 ; and --SO2 NR15 R15 ; wherein R15 is selected from H, aryl, alkyl, and alkyl substituted with halogen; --OH, phenoxy, aryl, --CN, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; X is --CO--, --COO--, or --SO2 --; R16 is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy; and when X is --CO--, R16 also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; phenoxy substituted with one or more of alkyl, carboxy, alkoxy, carbalkoxy, or halogen; R1 and R2 can be a single combined group such as pentamethylene, tetramethylene, ethyleneoxyethylene, ethylene sulfonylethylene, or ##STR145## which, with the nitrogen to which it is attached, forms a ring; R17 is alkyl, aryl, or cycloalkyl;
R3 is alkylene, arylene, aralkylene, alkyleneoxy, or alkyleneoxyalkylene;
Z is a direct single bond, OCO, O, S, SO2, R17 SO2 N═, ##STR146## arylene, or alkylene; R4, R5, and R6 are each selected from hydrogen or alkyl;
R7 is carboxy, carbalkoxy, or (R)n ;
R10 is hydrogen, alkyl, and aryl;
R8 and R9 are each selected from hydrogen and substituted or unsubstituted alkyl, aryl, or cycloalkyl
R11 and R12 are each selected from hydrogen, alkyl, hydroxyl, or acyloxy;
B represents the atoms necessary to complete a five- or six-membered ring and is selected from ##STR147## each P and Q is selected from cyano, carbalkenyloxy, carbcycloalkyloxy, carbalkoxy, carbaryloxy, carbaralkyloxy, carbamyl, carboxy, N-alkylcarbamyl, N-alkyl-N-arylcarbamyl, N,N-dialkylcarbamyl, N-arylcarbamyl, N-cyclohexylcarbamyl, aryl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, naphthyl, pyridyl, pyrimidinyl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl, SO2 alkyl, SO2 aryl, and acyl, or P and Q may be combined as ##STR148## wherein R17 is defined above and R18 is CN, COOH, CO2 alkyl, carbamyl, or N-alkylcarbamyl;
wherein at least one of A, P, and Q for each dye molecule must be or bear a condensable group selected from carboxy, carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy, N-(alkyl)2 carbamyloxy, amino, alkylamino, hydroxyl, N-phenylcarbamyloxy, cyclohexanoyloxy, and carbocyclohexyloxy;
wherein when an (R) substituent is present, n is an integer up to the available substitution sites on the ring; and
wherein in the above definitions, each alkyl, aryl, or cycloalkyl moiety or portion of a group or radical may be substituted with hydroxyl, acyloxy, alkyl, cyano, alkoxycarbonyl, halogen, alkoxy, or aryl, aryloxy, or cycloalkyl.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/153,299 US4804719A (en) | 1988-02-05 | 1988-02-05 | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
| EP89902159A EP0400038A1 (en) | 1988-02-05 | 1989-02-02 | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
| JP1502011A JPH03502339A (en) | 1988-02-05 | 1989-02-02 | Water-dissipating polyesters and polyester-amides with copolymerized colorants |
| PCT/US1989/000405 WO1989007118A1 (en) | 1988-02-05 | 1989-02-02 | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
| CA000590040A CA1323461C (en) | 1988-02-05 | 1989-02-03 | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/153,299 US4804719A (en) | 1988-02-05 | 1988-02-05 | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4804719A true US4804719A (en) | 1989-02-14 |
Family
ID=22546600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/153,299 Expired - Lifetime US4804719A (en) | 1988-02-05 | 1988-02-05 | Water-dissipatable polyester and polyester-amides containing copolymerized colorants |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4804719A (en) |
| EP (1) | EP0400038A1 (en) |
| JP (1) | JPH03502339A (en) |
| CA (1) | CA1323461C (en) |
| WO (1) | WO1989007118A1 (en) |
Cited By (69)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US5043376A (en) * | 1990-02-26 | 1991-08-27 | Eastman Kodak Company | Liquid-dispersible, polymeric colorant compositions and aqueous dispersions |
| US5006598A (en) * | 1990-04-24 | 1991-04-09 | Eastman Kodak Company | Water-dispersible polyesters imparting improved water resistance properties to inks |
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| US5876463A (en) * | 1995-06-07 | 1999-03-02 | Bristol-Myers Squibb Company | Compositions for coloring keratinous fibers comprising sulfo-containing, water dispersible colored polymers |
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| US5744129A (en) * | 1996-05-28 | 1998-04-28 | Dobbs; Suzanne Winegar | Aqueous lip gloss and cosmetic compositions containing colored sulfopolyesters |
| US6344497B1 (en) | 1996-10-01 | 2002-02-05 | Avecia Limited | Aqueous ink compositions |
| US6235096B1 (en) | 1996-10-01 | 2001-05-22 | Zeneca Limited | Aqueous ink compositions |
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| WO1998023689A1 (en) * | 1996-11-27 | 1998-06-04 | Eastman Chemical Company | 1,5(8)-bis(substituted-n-propylamino)-4,8(5)-bis(arylthio) anthraquinone compounds |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH03502339A (en) | 1991-05-30 |
| EP0400038A1 (en) | 1990-12-05 |
| WO1989007118A1 (en) | 1989-08-10 |
| CA1323461C (en) | 1993-10-19 |
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